Manufacture of photographic silver halide emulsions



Patented Jan. 9, 1940 UNITE STATES PAT MANUFACTURE OF PHOTOGRAPMC SEWER HALIDE EMULSIONS No Drawing. Application August 5, 1938, Serial No. 94,340. In Germany August 7, 1935 21 Claims.

Our present invention relates to the manufacture of silver halideemulsion layers.

A known method of producing photographic pictures in color consists in using photographic emulsions which contain dyestufi components adapted during the development to form dyestuffs with the products of oxidation of the developer used. Dyestufi components which are suitable for this method are named in U. S. Patents Nos. 1,102,028 and 1,055,155. When photographic layers containing these components are treated with developers which have a free amino-group, for example para phenylene diarnine, para dimethylamino-aniline, or ethoxy-para-dimethylamino-aniline, a picture in color is obtained. When films carrying more than one layer are used for producing multi-colored pictures there is the disadvantage in many cases that the dyestufi component of one layer, either during the appli- 20 cation of further layers or during the development of the composite material, difiuse into the other layers. For the production of faultless multi-colored pictures it is necessary to fix the several dyestufi components each in its own layer and to prevent any difiusion into adjacent layers. The materials hitherto known do not fulfill this condition.

Iii)

It is therefore an object of the present inven- A further object of the invention is to providea color photographic multi-layer material comprising a series of superimposed emulsion layers, each layer containing a dyestuif component which is fast to diffusion.

Further objects will be apparent from the detailed specification following hereinafter.

This invention is based on the observation that the diffusion of the dyestuif components may be 'Ininimized or completely suppressed by using as the component in the manufacture of the-photographic silver halide emulsion a dyestuff component of the type more narrowly defined below which has in its molecule an aliphatic carbon chain of more than 5 carbon atoms. The carbon chain may also comprise any substituentsand may be derived from an aliphatic unsaturated hydrocarbon.

As dy estufi' components which in a solution alkaline with sodium carbonate or caustic alkali react with the oxidation products of the developer may be named, for example, phenols, naphthols, amino-naphthols, aniline, naphthylamines; also all bodies which contain a reactive methylene group, for instance an aceto-acetic acid ester, a cyano-acetic acid ester, a benzoyl acetic acid ester, benzoylaceto-nitrile, hydrindene, pyrazolones, coumarone, hydroxythionaphthenes and the like. The introduction into these dyestufl components of an aliphatic carbon chain of more than 5 carbon atoms may be brought about in known manner to produce a homopolar linkage between the aliphatic carbon chain and color former. For example a union, like that in an acid 'amide, may be produced by introducing into an amino-group of the dyestufl component the radical of an aliphatic acid having more than 5 carbon atoms, for instance caprylic acid, lauric acid, undecylic acid, stearic acid, palmitic acid, oleic acid, erucic acid, melissic acid, cerotic acid, and stearolic acid, or by combining an acid group of the dyestufl? component with an aliphatic amine containing more than 5 carbon atoms, for instance octodecylamine, n-octylamine, secondary-octylamine, stearylamine, caprylamine, hexadecylamine, dodecylamine, undecylamine, hexadecyleneamine and cetylamine. Furthermore, an hydroxy-group in the dyestuff component may be acylated by means of an aliphatic chloride having more than 5 carbon atoms, for instance, the chloride of one of the above enumerated acids, or the dyestufl component may be synthesized from parent materials which already contain an aliphatic carbon chain of more than 5 carbon atoms. r

Especially valuable dyestufi forming components are obtained if the aforementioned dyestufl! components contain besides an aliphatic carbon chain of more than 5 carbon atoms one or more groupings which render the compounds water soluble, for instance, the carboxyl group,.the sulfonic acid group, the thiosulfonic acid group,

the arsenic acid group and several hydroxy groups. The advantage of the use of such components containing a grouping making them fast to diffusion and a grouping rendering them soluble in water resides in the fact that these components can be added to the solution of colloid at any stage of the preparation of the emulsion in a neutral aqueous solution or in theform of a salt, whereupon the component can no longer be removed from the colloid by washing with water or is no longer removed in the photographic treating baths. Such components containing besides an aliphatic chain with more than carbon atoms making the component fast to' diffusion a grouping rendering the component water soluble are, for instance, l-stearylamino- 4-:z-hYdIOXY- naphthoylaminobenzene 3 -sulionic acid, l-laurylamino i oz hydroxy-naphthoylaminonaphthalene-G-sulfonic acid, -undecylaminobenzoyl acetic 1C4 aminophenylglycin, m stearlylaminobenzoylacetanilide p carbonic acid, 1-(3'-sulfophenyl) 3 (4"-stearylaminophenyl) 5 pyrazolone, 1 (5-sulfo=-3'-stearylamino-phenyl)-3-methyl-5-pyrazolone, the sodiium salt of 1-octodecylamino-l-a-hydroxynaphthoylaminobenzene-3-thiosulfonic acid, and 1-a-hydroXy-naphthylamino 4 benzoyl-laurylaminobenzene-3-arsenic acid.

The grouping which renders the components water soluble, for instance, the sulfonic acid group orthe carboxyl group, may also be introduced in the aliphatic radical which latter is introduced for making the component fast to diffusion. Particularly suitable are such dyestufi components having in the aliphatic radical a double bond, since these double bonds can easily be sulfonated under such conditions that sulfonation at an undesired place is with certainty excluded. Another possibility of introducing a grouping which renders the dyestuff component water soluble into the aliphatic radical consists in reacting the amino group of a dyestuif component containing an amino group with a halogen fatty acid halide and exchanging the halogen atom in the fatty acid radical for a sulfo group by boiling with sodium sulfite.

A dyestufi component thus obtained may be introduced into the photographic emulsion at any stage of its production. The component is retained very firmly in the layer cast from the emulsion and the diffusing capacity of the component is the more diminished the higher is the number of carbon atoms in the aliphatic chain. If one selects a sufficiently large aliphatic radical, for example that of stearic acid, any diffusion of the dyestufi' component during the application of the layers or during the development of the finished composite photographic material may be completely prevented. Only with the use of emulsion layers of the kind described is the complete prevention of diffusion of the dyestuft component possible; multiple-color photographic.

pictures free from objection may be made when these layers are used.

The following examples illustrate the invention:

Example 1.--1 mol. of l-(para-aminophenyD- 3-methyl-5-pyrazolone (either free or in the form offhydrochloride) is dissolved in dry pyridine and 1 mol. of stearic acid chloride is added. After heating for 1 hour on the water-bath the product is isolated by pouring the mass into water. 4 grams of this l-(para-stearyl-aminophenyl)-3-methyl-5-pyrazolone are dissolved in 3 cc. of caustic soda lye of 20 per cent strength and about 50 cc. of water. and the solution is added to 1000 grams of a photographic silver halide emulsion.

Example 2.1 mol. of l-(meta-aminophenyl)- 3-methyl-5-pyrazolone is dissolved in dry pyridine and there is added 1 mol. of oleic acid chloride. After warming for an hour on the waterbath the product is isolated by pouring the mass into water. 4 grams of this l-(meta-oleylaminophenyl)-3-methyl-5-pyrazolone are dissolved in 3 cc. of caustic soda lye of 20 per cent strength and 50 cc. of water and the solution is added to 1000 grams of a silver halide emulsion.

Example 3.-l mol. of octodecylamine is dissolved in dry pyridine and 1 mol. of l-hydroxy- Z-naphthoylchloride is added. After heating for 1 hour on the water-bath the product is isolated by pouring the mass into water. 4: grams of this 'octodecyl-1-hydroxy-Z-naphthoylamine are dissolved in 5 cc. of caustic soda lye of 20 per cent strength and about 50 cc. of methanol and the solution is added to 1000 grams of photographic silver halide emulsion.

The multi-layer film ismade, for example, as

follows:

There is first applied to the support a silver halide emulsion panchromatically sensitized and containing per kilo grams of oct'odecyl-lhydroxy-2-naphthoylamine.

There is then applied directly an emulsion layer orthochromatically sensitized .and containing, per kilo, 10 grams of l-(meta-stearylaminophenyl) -3-methyl-5-pyrazolone.

Then follows an intermediate layer which contains a yellow dyestufl' capable of being washed out or bleached out.

Finally, there is applied an emulsion layer nonsensitized for color, which contains per kilo of emulsion 10 grams of decanoyl-p-aminobenzoylacetic acid-para-anisidide.

The layers of emulsion may be applied in any other order. Filter layers may also be used.

Example 4.--p-Aminobenzoylacetanilide is converted into p-lauryl-aminobenzoylacetanilide by means of lauryl chloride. 5 grams of p-laurylaminobenzoylacetanilide and 2 cc. of a caustic soda solution of 50 per cent strength are dissolved in 50 cc. of methanol and the solution is added to 1 kilo of a silver halide gelatin emulsion. The photographic layers cast from this emulsion yield a yellow dyestuff picture after developing with p-diethylaminoaniiine.

Example 5.-m-Aminobenzoylacetanilide pcarbonic acid is converted into m-stearylaminobenzoylacetanilide-p'-carbonic acid by means of stearic acid chloride. 5 grams of m-stearylaminobenzoylacetanilide-p'-carbonic acid and 5 cc. of a caustic soda solution of 20 per cent strength are dissolved in 50 cc. of methanol and added to 1 kilo of a silver halide emulsion. Photographic layers cast from this emulsion yield after development with p-diethylaminoaniline a yellow dyestufl picture.

Example 6.--1 molecular proportion of phenylhydrazine-B-sulfor'ric acid is condensed by means of 1 molecular prcportio'n of p-nitro-benzoylacetic acid ester to l-(3'-suliophenyl)-3-(4"- nitrophenyl) -5-pyrazolone and this compound is reduced according to known methods to 1-(3'- sulfophenyl) 3 (4 aminophenyl) 5 -pyrazolone. The amino group of this compound is furthermore linked to stearic acid. 10 grams of the sodium salt of 1-(3-sulfophenyl')-3-(4-stearylaminophenyl) -5-pyrazolone are dissolved in 50 cc. of water and added to 1 kilo of a silver halide emulsion. Photographic layers cast from this emulsion yield after development with p'diethylaminoanlline a red dyestuii' picture with a cast to blue.

Example 7.-1 (m-stearylaminophenyl) 3 methyl-E-pyrazolone of Example 3 is sulfonated in concentrated sulfuric acid by means of 15 per cent of fuming sulfuric acid. In this reaction the sulfur group probably enters the meta-position with relation to the acylamino group. 10 grams of the sodium salt of 1-(5'-sulfo-3- stearylaminophenyl)-3-methyl-5-pyrazolone are dissolved in 50 cc. of water and added to 1 kilo of the silver halide emulsion. Photographic layers cast from this emulsion yield by development with p-diethylaminoaniline a red dyestuil picture with a cast te yellow.

Example 8.--Aminophenolmethylpyrazolone is condensed with oleic acid chloride and the condensation product is sulfonated. When this product is added to a photographic silver halide emulsion, a layer cast from said emulsion is developed a red tint with p-dimethylaminoaniline after exposure.

Example ,9.a-hydroxynaphthoic acid chloride is condensed with oleyl amine and the product of condensation'is sulfonated. A photographic silver halide emulsion layer containing the condensation product is developed a blue tint after 'exposure.

Example 10.--p-aminobenzoylacetanilide is condensed with a-bromostearic acid bromide and the condensation product is boiled with sodium sulfite. A photographic silver halide emulsion layer containing the product is developed a yellow tint after'exposure.

The photographic layers containing a dyestufi component rendered fast against diffusion may be quite generally applied for the purpose of color. photography. They may be applied in all proc-- been hitherto used for the same purpose, is based on the fact that the compounds in accordance with the present invention are absolutely fast to diffusion, even if they are most easily soluble in water, and that a carbon chain in accordance with the invention may be easily introduced into any dyestufi intermediate product molecule with out impairing thereactivity of this molecule.

The following examples are illustrative of the appliance of layers in accordance with the invention for different color photographic processes.

Example 11.1 kilo of silver bromide emulsion is mixed with an aqueous solution of 15 grams of the sodium salt of 4"-stearylaminobenzoyl-3'- aminobenzoyl l-amino-8-hydroxynaphthalene 3.6-disulfonic acid. This emulsion is cast on a support to form a photographic layer. After exposure, development and fixing the silver picture is made in known manner into a dianisidineantitetraazotate picture. When immersing this antitetraazotate silver picture in' a dilute acid, a pure blue azo dyestuff picture is produced.

If instead of the H-acid derivative the 4"- stearylaminobenzoyl 3-aminobenzoyl-2-amino- 5-naphthol-7-sulfonic acid is used, a blue-red dyestufi picture is obtained. If the condensation product from bromostearlc acid bromide p amino-acetoacetic acid anilide which boiled with sodium sulfite is used. a yellow stufl picture is obtained.

It is obvious that by suitable sensitization and 5 application of these three layers to a single support there is obtained a photographic material for color photography whereby it is not neces sary to use for all three layers an emulsion which has been pretreated in the manner indicated. 7 For instance, it is possible to arrange the layers yielding the red picture and the yellow picture produced according to the above example on one side of the support, whereas the other side of the support is coated with an emulsion which does not contain any component and in which the dyestufi picture is produced according to one of the well known processes, for instance, by toning.

layers containing the componentsmay be dyed with a suitable filtering dye.

Example 12.According to a. modification an amine capable of being diazotized is contained in the gelatin or silver halideemulsion, for instance, p-aminododecylbenzene or o-aminosulfooleylbenzene, and the silver picture is in known manner converted into an insoluble nitrite compound. Ii diazotation is started in optional manner, a dyestuff picture is obtained in the presence of a second azo coupling component. This second azo component can however be contained in the layer together with the amine capable of diazotation and may have been made fast to diffusion in any manner.

Example 13.1 kilo of silver bromide emulsion is mixed with an aqueous solution of the sodium salt of 6-undecy1-2-hydroxy-l-benzoic acid, and this emulsion is made into photographic layers. After development, fixing and bleaching of a silver picture produced in this layer, the diazo compound from 4-aminodiphenylamine is in known. manner adsorbed at the silver ferrocyanide. After washing, coupling is effected by immersing the photographic layer in a. soda solution of 1 per cent strength and a yellow dyestuff picture is obtained. It is also possible to add to the emulsion at any stage before casting the fatty acid amide of an aminated leuco compound, for. instance, of an aminoindoxyl, and this may be oxidized to a dyestufl by treatment with lead chromate.

The reactions of the above examples must not be carried out by means of the silver picture. It is also possible to harden the silver halide emulsion containing the dyestufi intermediate products rendered fast against diffusion at the places occupied by the silver picture or at the places free from a metal precipitate, and then to produce the dyestuif picture in suitable manner at the hardened or unhardened places by azo coupling or by oxidation.

What We claim is:

1. A photographic silver halide emulsion containing a color former fast to diffusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine-, azomethine, and azo dyestuffs, and having an alkyl radical of a carbon chain of more than 5 carbon atoms linked to an atom of its molecule by a homopolar linkage.

2. A photographic silver halide emulsion con- 75 taining a color former fast to diffusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine-, azomethine, and azo dyestuils, and having an alkyl radical of an unsaturated carbon chain of more than carbon atoms linked to an atom of its molecule by a homopolar linkage.

3. A photographic silver halide emulsion containing a color former fast to diffusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine-, azomethine, and azo dyestuffs, and having an alkyl radicle of a substituted carbon chain of more than 5 carbon atoms linked to an atom of its molecule by a homopolar linkage.

4. A photographic silver halide emulsion containing a color former fast to difiusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine, nzornethine, and azo dyestufis, said color former having an alkyl radical of a carbon chain of more than 5 carbon atoms linked to an atom of its molecule by a homopolar linkage, and being substituted by a substituent whichimparts solubility in water to said color former.

5. A photographic silver halide emulsion containing a color former fast to diifusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine, azomethine--, and azo dyestuffs, said color former having an alkyl radical of a carbon chain of more than 5 carbon atoms linked to an atom of its molecule by a homopolar linkage, and being substituted by at least one radical selected from the group consisting of carboxylic acid, sulfonic acid-, thiosulfonic acid-, arsenic acid-, and hydroxyl radicals.

6. A photographic silver halide emulsion containing a color former fast to diffusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine-, azomethine. and azo dyestufis, said color former having in its molecule an amino group substituted by an aliphatic acyl radical having a carbon chain of more than 5 carbon atoms.

'7. A photographic silver halide emulsion containing a color former fast to diffusion, said color former being capable of forming a dye selected from the group consisting of quinoneimine, azomethine, and azo dyestuffs, said color former having in its molecule an acid group substituted by an alkyl-amino radical having a carbon chain of more than 5 carbon atoms.

8. A silver halide gelatin emulsion for color photography, containing a color former fast to diffusion with respect to the gelatin, said color former being capable of forming a dyestufi selected from the group consisting of quinoneiminc-, azomethine-, and azo dyestuffs in situ with a silver picture upon being contacted with a color forming developer, and having an alkyl radical of a carbon chain of 11 to 18 carbon atoms linked to an atom of its molecule by a homopolar linkage.

9. A silver halide gelatin emulsion for color photography containing a color former fast to diffusion with respect to the gelatin, said color former being capable of forming a dyestufl selected from the group consisting of quinoneimine, azomethine, and azo dyestufis in situ with a silver picture upon being contacted with a color forming developer, and having an alkyl radical of an unsaturated carbon chain of more than 5 carbon atoms linked to an atom of its molecule by a homopolar linkage, said carbon chain being substituted by radicals which impart solubility in water to said color former.

10. A silver halide gelatin emulsion for color photography containing a color former fast to diffusion with respect to the gelatin, said color former being capable of forming a dyestuff selected from the group consisting of quinoneimine-, azomethine, and azo dyestuffs in situ with a silver picture upon being contacted with acolor forming developer, said color former containing in its molecule an amino radical substituted by an aliphatic acid radical with a chain of from 11 to 18 carbon atoms.

11. A silver halide gelatin emulsion for color photography containing a color former fast to diffusion with respect to the gelatin, said color former being capable of forming a dyestufl selected from the group consisting of quinoneimine, azomethine--, and azo dyestuffs in situ with a silver picture upon being contacted with a color forming developer, said color former containing in its molecule an acid radical substituted by the radical of an aliphatic amine with a carbon chain of 11 to 18 carbon atoms.

12. A color photographic light-sensitive element comprising a support and a plurality of superposed silver halide gelatin emulsion layers, each layer containing a color former fast to difiusion with respect to the gelatin, said color former being capable of forming a dyestuff selected from the group consisting of quinoneimine-, azomethine-, and azo dyestuffs in situ with a silver picture upon being contacted with a color forming developer, and having an alkyl radical of a carbon chain of 11 to 18 carbon atoms linked to an atom of its molecule by a homopolar linkage.

13. A silver halide gelatin emulsion layer containing as a color former 1-(5'-sulfo-3'-stearylaminophenyl) -3-methyl-5-pyrazolone.

14. A silver halide gelatin emulsion layer containing the sulfonated condensation product of amino-phenyl-methyl pyrazolone with oleic acid chloride.

15. A photographic silver halide emulsion containing a color former fast to diffusion, said color former being capable of forming a dye selected from the group consisting of quinoneamine-, azomethine, and azo dyestuffs, and having an alkyl radicle of a carbon chain of more than 5 carbon atoms linked to an atom of its molecule by a linkage selected from the class consisting of a carbon to carbon linkage, an ester linkage and an acid amide linkage.

16. A photographic silver halide emulsion as defined in claim 15, wherein said carbon chain is unsaturated.

17. A photographic silver halide emulsion as defined in claim 15, wherein said carbon chain is substituted.

18. A photographic silver halide emulsion as defined in claim 15, wherein said color former is substituted by a substituent which imparts solubility in water thereto.

19. A photographic silver halide emulsion as defined in claim 15 wherein said color former is substituted by at least one radicle selected from the group consisting of carboxylic acid. sulphonic acid, thiosulphonic acid--, arsenic acidand hydroxyl radlcles.

20. A photographic silver halide emulsion as defined in claim 15 wherein the color former is capable of producing the dyestuff by color forming development and wherein said carbon chain contains from 11 to 18 carbon atoms.

21. A photographic silver halide emulsion as defined in claim 15, wherein said color former is capable of producing the dyestufl by color forming development, wherein said carbon chain contains from 11 to 18 carbon atoms and is substituted by radicals imparting solubility in water to said color former. a GUSTAV WILMANNS.

KARL KUMETAT. ALFRED FRGHLICH. WILHELM SCHNEIDER. RICHARD BRODERSEN. 

